CN109346656B - Application of organic coating, pole piece for lithium ion battery and application thereof, lithium ion battery and application thereof - Google Patents

Application of organic coating, pole piece for lithium ion battery and application thereof, lithium ion battery and application thereof Download PDF

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Publication number
CN109346656B
CN109346656B CN201811195034.5A CN201811195034A CN109346656B CN 109346656 B CN109346656 B CN 109346656B CN 201811195034 A CN201811195034 A CN 201811195034A CN 109346656 B CN109346656 B CN 109346656B
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lithium ion
solvent
coating
ion battery
parts
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CN109346656A (en
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唐永炳
许天军
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Real Power Industrial Ltd
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Real Power Industrial Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides an application of an organic coating, a pole piece for a lithium ion battery and an application thereof, and the lithium ion battery and an application thereof, and belongs to the technical field of lithium ion batteries. The invention provides an application of an organic coating as a diaphragm in the preparation of a lithium ion battery; the organic coating is formed by curing a coating, and the coating comprises the following components in parts by weight: 9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent. The invention also provides a pole piece coated with the organic coating for the lithium ion battery, and the lithium ion battery comprising the pole piece. The organic coating has a microporous structure, has good wettability to electrolyte, can reduce internal resistance and improve the electrochemical performance of the battery, and the lithium ion battery obtained by the pole piece coated with the organic coating can be free of a diaphragm, so that the space utilization rate in the lithium ion battery cell is greatly improved, and the volume energy density of the lithium ion battery is improved.

Description

Application of organic coating, pole piece for lithium ion battery and application thereof, lithium ion battery and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to application of an organic coating, a pole piece for a lithium ion battery and application thereof, and the lithium ion battery and application thereof.
Background
The lithium ion battery has the characteristics of high voltage, long cycle life, no pollution and the like, and is widely applied to the fields of smart phones, digital cameras, notebook computers, new energy electric vehicles and the like. With the development of digital products towards lighter and thinner, the requirements of new energy electric vehicles on endurance mileage are continuously increased, and the products all put higher and higher requirements on the energy density of lithium ion batteries.
The current lithium ion battery structure mainly comprises a positive plate, a negative plate, a diaphragm and electrolyte. Any adjacent positive plate and negative plate are separated by a diaphragm. The diaphragm is used as an important component of the current lithium ion battery, is a high-molecular functional material or a composite material with a microporous structure, is a high value-added material with a higher technical barrier in lithium ion battery materials, comprises a matrix material such as polyethylene and polypropylene materials, a composite material of the polyethylene and the polypropylene materials and the like, and has the main functions of separating the anode and the cathode of the battery, absorbing electrolyte and only passing lithium ions but not electrons.
The existing commercial lithium ion batteries are provided with diaphragms, but the existence of the diaphragms not only increases the complexity in the production process, but also increases the cost, and in addition, due to the limitation of the manufacturing process, the diaphragms which are the parts which have small contribution to the battery capacity occupy more volume inside the lithium ion batteries, so that the volume energy density of the lithium ion batteries is limited, and the lithium ion batteries are not beneficial to the development towards high energy density.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide the application of an organic coating as a diaphragm in the preparation of a lithium ion battery; the organic coating is used for preparing the lithium ion battery instead of the diaphragm, so that the lithium ion battery can be provided with no diaphragm, and the problems can be overcome or the technical problems can be at least partially solved.
The second purpose of the invention is to provide a pole piece for a lithium ion battery; the pole piece for the lithium ion battery is coated with the organic matter coating, and the microporous structure of the organic matter coating has good wettability to the electrolyte, so that the internal resistance can be reduced, and the electrochemical performance of the battery can be improved.
The invention also aims to provide the application of the pole piece for the lithium ion battery in the lithium ion battery; the pole piece for the lithium ion battery coated with the organic coating is applied to the lithium ion battery, and realizes the diaphragm-free formation of the lithium ion battery, so that the battery preparation process is simple, and the battery cost is reduced.
The fourth purpose of the invention is to provide a lithium ion battery; the lithium ion battery is not provided with a diaphragm, so that the space utilization rate inside the lithium ion battery cell is greatly improved, and the volume energy density of the lithium ion battery is improved.
The fifth purpose of the invention is to provide the application of the lithium ion battery in smart phones, digital cameras, notebook computers or electric vehicles, and the lithium ion battery without the diaphragm can make digital products develop towards lighter and thinner directions, so that the endurance mileage of new energy electric vehicles is improved.
In a first aspect, an organic coating is provided for use as a separator in the preparation of a lithium ion battery;
the organic coating is formed by curing a coating, and the coating comprises the following components in parts by weight:
9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent.
Preferably, the coating comprises the following components in parts by weight:
9.5-10.5 parts of vinylidene fluoride-hexafluoropropylene copolymer, 110 parts of solvent 100 and 17-34 parts of non-solvent.
Preferably, the solvent is an organic solvent, preferably at least one of acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide, and more preferably acetone;
preferably, the non-solvent is an alcoholic solvent, preferably C1-C4The alcohol solvent of (3) is more preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and still more preferably ethanol.
Preferably, the vinylidene fluoride-hexafluoropropylene copolymer, the solvent and the non-solvent are mixed uniformly to obtain the coating;
preferably, at the temperature of 45-52 ℃, adding the vinylidene fluoride-hexafluoropropylene copolymer into the solvent to obtain a mixed solution of the vinylidene fluoride-hexafluoropropylene copolymer and the solvent after 1-1.5h, then adding the non-solvent to obtain the coating after 0.5-1 h.
In a second aspect, a pole piece for a lithium ion battery is provided, which includes a current collector, wherein an active material layer is coated on the surface of the current collector, an organic coating is further coated on the surface of the current collector, and the active material layer is located between the organic coating and the current collector;
wherein the organic coating is formed by curing a coating;
the coating comprises the following components in parts by weight:
9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent.
Preferably, the coating comprises the following components in parts by weight:
9.5-10.5 parts of vinylidene fluoride-hexafluoropropylene copolymer, 110 parts of solvent 100 and 17-34 parts of non-solvent;
preferably, the solvent is an organic solvent, preferably at least one of acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide, and more preferably acetone;
preferably, the non-solvent is an alcoholic solvent, preferably C1-C4The alcohol solvent of (3) is more preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and still more preferably ethanol.
Preferably, the pole piece is a positive pole piece or a negative pole piece;
preferably, the coating method of the organic coating is one or a combination of more than two of a doctor blade coating method, a spray coating method, a roll coating method, a casting coating method and a gravure printing method;
preferably, the organic coating has a thickness of 5 to 30 μm.
In a third aspect, an application of the pole piece for the lithium ion battery in the lithium ion battery is provided.
The fourth aspect provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode and the negative electrode are assembled into a battery roll core in a winding or laminating manner, and the positive electrode piece and/or the negative electrode piece are/is the electrode piece for the lithium ion battery.
In a fifth aspect, an application of the lithium ion battery in a smart phone, a digital camera, a notebook computer or an electric vehicle is provided.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides an application of an organic coating as a diaphragm in the preparation of a lithium ion battery, wherein the organic coating is formed by curing a coating, and the coating comprises a vinylidene fluoride-hexafluoropropylene copolymer with a specific dosage, a solvent and a non-solvent. The vinylidene fluoride-hexafluoropropylene copolymer introduces Hexafluoropropylene (HFP) into polyvinylidene fluoride (PVDF), so that the crystallinity of the polyvinylidene fluoride (PVDF) can be reduced, and the electrolyte adsorption capacity of the organic coating can be improved.
2. The organic coating is formed by curing a coating, wherein the coating comprises a vinylidene fluoride-hexafluoropropylene copolymer, a solvent and a non-solvent, when the coating is cured into the organic coating, the solvent in the coating is firstly evaporated, so that the content of the vinylidene fluoride-hexafluoropropylene copolymer and the non-solvent is increased, the coating begins to phase separate to generate a rich phase and a poor phase of an organic polymer, the content of the solvent in the rich phase is low, the vinylidene fluoride-hexafluoropropylene copolymer can be precipitated to form a membrane framework, at the moment, the poor phase still contains more non-solvent, after the non-solvent contained in the poor phase in the membrane framework is volatilized, a small amount of the vinylidene fluoride-hexafluoropropylene copolymer contained in a poor phase solution can be crystallized, contracted and attached to the framework to form micropores, so that the organic coating with a micropore structure is obtained, and the micropore structure of the organic coating has good wettability to an electrolyte, can reduce internal resistance and improve the electrochemical performance of the battery.
3. The organic coating is used as the diaphragm for preparing the lithium ion battery, and the organic coating coated on the surface of the lithium ion battery pole piece replaces the diaphragm, so that the lithium ion battery can be free from the diaphragm, the space utilization rate inside the lithium ion battery cell is greatly improved, and the volume energy density of the lithium ion battery is improved.
4. The organic coating is used as the diaphragm for preparing the lithium ion battery, so that the diaphragm-free lithium ion battery is realized, the preparation process of the battery is simple, the battery cost is reduced, and meanwhile, the coated organic coating is more tightly combined with the pole piece, so that the electrochemical performance of the battery is favorably improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic cross-sectional structure diagram of a positive electrode and a negative electrode provided in embodiment 1 of the present invention;
fig. 2 is a schematic cross-sectional structure diagram of the positive and negative electrodes provided in embodiment 2 of the present invention;
fig. 3 is a schematic cross-sectional structure diagram of the positive electrode and the negative electrode provided in embodiment 3 of the present invention.
Icon: 1-copper foil base; 2-a negative electrode active material layer; 3-an organic coating on the surface of the negative active material layer; 4-aluminum foil substrate; 5-positive electrode active material layer; 6-organic coating on the surface of the positive active material layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples and drawings, but those skilled in the art will understand that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, an organic coating is provided for use as a separator in the preparation of a lithium ion battery;
the organic coating is formed by curing a coating, and the coating comprises the following components in parts by weight:
9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent.
By mixing the vinylidene fluoride-hexafluoropropylene copolymer with the solvent and the non-solvent, when the coating is cured into an organic coating, the solvent in the coating is firstly evaporated, the content of the vinylidene fluoride-hexafluoropropylene copolymer and the non-solvent is increased, the coating begins to phase separate to generate a rich phase and a poor phase of the organic polymer, the content of the solvent in the rich phase is low, the vinylidene fluoride-hexafluoropropylene copolymer can precipitate to form a film framework, at this time, the lean phase still contains a large amount of the non-solvent, and when the non-solvent contained in the lean phase in the membrane skeleton is volatilized, a small amount of vinylidene fluoride-hexafluoropropylene copolymer contained in the lean phase solution can be crystallized and shrunk to be attached to the framework to form micropores, therefore, the organic coating with the microporous structure is obtained, and the microporous structure of the organic coating has good wettability to the electrolyte, so that the internal resistance can be reduced, and the electrochemical performance of the battery can be improved.
The organic coating is used as the diaphragm for preparing the lithium ion battery, and the organic coating coated on the surface of the lithium ion battery pole piece replaces the traditional diaphragm, so that the lithium ion battery can be free of the diaphragm, the space utilization rate inside the lithium ion battery cell is greatly improved, and the volume energy density of the lithium ion battery is improved.
The organic coating is used as the diaphragm for preparing the lithium ion battery, so that the diaphragm-free lithium ion battery is realized, the preparation process of the battery is simple, the battery cost is reduced, and meanwhile, the coated organic coating is more tightly combined with the pole piece, so that the electrochemical performance of the battery is favorably improved.
In the vinylidene fluoride-hexafluoropropylene copolymer, "-" means "and", that is, a copolymer obtained by copolymerizing vinylidene fluoride and hexafluoropropylene.
It can be understood that when the coating is solidified into an organic coating, the solvent in the coating is firstly evaporated, the vinylidene fluoride-hexafluoropropylene copolymer is precipitated to form a membrane framework, then the non-solvent is volatilized, and the residual vinylidene fluoride-hexafluoropropylene copolymer can be crystallized, contracted and attached to the framework to form micropores, so that the organic coating with a micropore structure is obtained. Therefore, the boiling point of the solvent used in combination is lower than that of the non-solvent.
It is understood that the solvent is a liquid capable of dissolving the vinylidene fluoride-hexafluoropropylene copolymer, and may be, for example, acetone; the non-solvent is a liquid which is not capable of dissolving the vinylidene fluoride-hexafluoropropylene copolymer but is miscible with the solvent, and may be, for example, ethanol or the like.
The vinylidene fluoride-hexafluoropropylene copolymer introduces Hexafluoropropylene (HFP) into polyvinylidene fluoride (PVDF), so that the crystallinity of the polyvinylidene fluoride (PVDF) can be reduced, and the electrolyte adsorption capacity of an organic coating obtained after the coating is cured is improved. By weight, 9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, and typical but non-limiting parts by weight of the vinylidene fluoride-hexafluoropropylene copolymer are 9 parts, 9.1 parts, 9.2 parts, 9.3 parts, 9.4 parts, 9.5 parts, 9.6 parts, 9.7 parts, 9.8 parts, 9.9 parts, 10 parts, 10.1 parts, 10.2 parts, 10.3 parts, 10.4 parts, 10.5 parts, 10.6 parts, 10.7 parts, 10.8 parts, 10.9 parts or 11 parts.
The solvent is liquid which can dissolve the vinylidene fluoride-hexafluoropropylene copolymer to generate a uniform mixture system, and the non-solvent is liquid which can not dissolve the vinylidene fluoride-hexafluoropropylene copolymer but can be mixed with the solvent. 90-120 parts of solvent and 15-40 parts of non-solvent by weight; typical but non-limiting parts by weight of solvent are 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, 106 parts, 107 parts, 108 parts, 109 parts, 110 parts, 111 parts, 112 parts, 113 parts, 114 parts, 115 parts, 116 parts, 117 parts, 118 parts, 119 parts or 120 parts; typical but non-limiting parts by weight of non-solvent are 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts or 40 parts.
As a further preferable technical scheme, the coating comprises the following components in parts by weight:
9.5-10.5 parts of vinylidene fluoride-hexafluoropropylene copolymer, 110 parts of solvent 100 and 17-34 parts of non-solvent.
In the preferred embodiment, by reasonably adjusting the amounts of the vinylidene fluoride-hexafluoropropylene copolymer, the solvent and the non-solvent, after the solvent is evaporated, a specific amount of the vinylidene fluoride-hexafluoropropylene copolymer precipitates to form a membrane framework, and a specific amount of the remaining specific amount of the vinylidene fluoride-hexafluoropropylene copolymer distributes in the membrane framework, after the non-solvent in the membrane framework is volatilized, the remaining specific amount of the vinylidene fluoride-hexafluoropropylene copolymer crystallizes and shrinks to be attached to the framework to form micropores, so that the organic coating with the micropore structure is obtained, and the micropore structure of the organic coating has good wettability to the electrolyte, so that the internal resistance can be reduced, and the electrochemical performance of the battery can be improved.
In a more preferred embodiment, the solvent is an organic solvent.
It is understood that the "organic solvent" herein refers to an organic solvent that can dissolve the vinylidene fluoride-hexafluoropropylene copolymer.
As a further preferable technical scheme, the solvent is at least one of acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide; in this preferred embodiment, acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide all dissolve the vinylidene fluoride-hexafluoropropylene copolymer to form a homogeneous mixture system.
As a further preferred technical solution, the solvent is acetone; in the preferred embodiment, acetone can rapidly dissolve the vinylidene fluoride-hexafluoropropylene copolymer, which is more beneficial to form a uniform mixture system, and the boiling point of the acetone is lower, is only 56.5 ℃, and is easy to evaporate, when the coating is cured into an organic coating, after the acetone serving as a solvent is evaporated, the contents of the vinylidene fluoride-hexafluoropropylene copolymer and a non-solvent are increased, the coating is subjected to phase separation, a rich phase and a poor phase of the organic polymer are generated, the content of the solvent in the rich phase is low, and at the moment, the vinylidene fluoride-hexafluoropropylene copolymer can be precipitated to form a film framework.
As a further preferred technical scheme, the non-solvent is an alcohol solvent; in the preferred embodiment, the alcohol solvent can not dissolve the vinylidene fluoride-hexafluoropropylene copolymer, but can be mixed with organic solvents such as acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetamide and the like, when the coating is cured into an organic coating, after the solvent is evaporated, the contents of the vinylidene fluoride-hexafluoropropylene copolymer and the alcohol solvent are increased, the vinylidene fluoride-hexafluoropropylene copolymer can not be dissolved by the alcohol solvent, the vinylidene fluoride-hexafluoropropylene copolymer can be precipitated to form a membrane framework, the alcohol solvent and the residual vinylidene fluoride-hexafluoropropylene copolymer are distributed in the membrane framework, after the alcohol solvent is volatilized, a small amount of the vinylidene fluoride-hexafluoropropylene copolymer contained in the poor phase solution can be crystallized and shrunk to be attached to the framework to form micropores, therefore, the organic coating with the microporous structure is obtained, and the microporous structure of the organic coating has good wettability to the electrolyte, so that the internal resistance can be reduced, and the electrochemical performance of the battery can be improved.
As a further preferred embodiment, the non-solvent is C1-C4Alcohol solvent of (a); typically but not limitatively, C1-C4The alcohol solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol or propylene glycol, etc. In the preferred embodiment, C1-C4The alcohol solvent (2) does not dissolve the vinylidene fluoride-hexafluoropropylene copolymer, but can be mixed with an organic solvent such as acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide.
As a further preferable technical solution, the non-solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; in this preferred embodiment, methanol, ethanol, N-propanol, isopropanol, N-butanol or isobutanol do not dissolve the vinylidene fluoride-hexafluoropropylene copolymer, but can be mixed with an organic solvent such as acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or dimethylacetamide.
As a further preferred technical solution, the non-solvent is ethanol; in the preferred embodiment, ethanol can not dissolve vinylidene fluoride-hexafluoropropylene copolymer, but can be mixed with organic solvent such as acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethylacetamide, when the coating is cured into an organic coating, after the solvent is evaporated, the content of vinylidene fluoride-hexafluoropropylene copolymer and ethanol is increased, the vinylidene fluoride-hexafluoropropylene copolymer can not dissolve the vinylidene fluoride-hexafluoropropylene copolymer, the vinylidene fluoride-hexafluoropropylene copolymer can precipitate to form a membrane framework, the ethanol and the residual vinylidene fluoride-hexafluoropropylene copolymer are distributed in the membrane framework, after the ethanol is volatilized, a small amount of vinylidene fluoride-hexafluoropropylene copolymer contained in the lean phase solution can be crystallized and contracted to be attached to the framework to form micropores, thereby obtaining the organic coating with a micropore structure, the microporous structure of the organic coating has good wettability to electrolyte, can reduce internal resistance and improve the electrochemical performance of the battery.
As a further preferred technical scheme, the coating is obtained by uniformly mixing the vinylidene fluoride-hexafluoropropylene copolymer, the solvent and the non-solvent; in the preferred embodiment, the preparation method is simple to operate, easy to implement, strong in operability and easy to realize large-scale production.
As a further preferable technical scheme, at the temperature of 45-52 ℃, adding the vinylidene fluoride-hexafluoropropylene copolymer into a solvent, obtaining a mixed solution of the vinylidene fluoride-hexafluoropropylene copolymer and the solvent after 1-1.5h, then adding a non-solvent, and obtaining the coating after 0.5-1 h; in the preferred embodiment, the temperature and time are reasonably adjusted to dissolve the vinylidene fluoride-hexafluoropropylene copolymer in the solvent, and then the vinylidene fluoride-hexafluoropropylene copolymer is uniformly mixed with the non-solvent to obtain the coating.
In a second aspect, a pole piece for a lithium ion battery is provided, which includes a current collector, wherein an active substance layer is coated on the surface of the current collector, an organic substance coating is further coated on the surface of the current collector, and the active substance layer is located between the organic substance coating and the current collector;
wherein the organic coating is formed by curing a coating;
the coating comprises the following components in parts by weight:
9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent.
It is understood that "curing" herein means that the coating loses the liquid portion and changes from a liquid state to a solid state, and that the coating loses the solvent and non-solvent and changes from a liquid coating to a solid coating.
The surface in the "active material layer is coated on the surface of the current collector" refers to the front surface and/or the back surface of the current collector, and may be coated on only one surface (front surface or back surface) or may be coated on both surfaces. Correspondingly, "the surface of the current collector is further coated with an organic coating" means that the surface coated with the active material layer is further coated with an organic coating, for example, if the front surface (only one surface) of the current collector is coated with the active material layer, the front surface is further coated with the organic coating, and the active material layer is located between the organic coating and the current collector.
The active material layer is divided into an active material layer of the positive electrode sheet and an active material layer of the negative electrode sheet. The active substance layer of the positive plate mainly comprises at least one of nickel cobalt aluminum, nickel cobalt manganese, lithium manganate, lithium iron phosphate and lithium cobaltate; the active material layer of the negative electrode sheet mainly includes at least one of graphite, silicon materials, and alloys.
The pole piece is coated with a coating formed by curing a specific coating, and the microporous structure of the coating has good wettability to electrolyte, so that the internal resistance can be reduced, and the electrochemical performance of the battery can be improved.
As a further preferable technical scheme, the coating comprises the following components in parts by weight: 9.5-10.5 parts of vinylidene fluoride-hexafluoropropylene copolymer, 110 parts of solvent 100 and 17-34 parts of non-solvent.
In a more preferred embodiment, the solvent is an organic solvent, preferably at least one of acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and dimethylacetamide, and more preferably acetone.
As a further preferred embodiment, the non-solvent is an alcoholic solvent, preferably C1-C4The alcohol solvent of (3) is more preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and still more preferably ethanol.
As a further preferable technical scheme, the pole piece is a positive pole piece or a negative pole piece.
As a further preferable embodiment, the coating method of the organic coating layer is one or a combination of two or more of a blade coating method, a spray coating method, a roll coating method, a cast coating method, and a gravure printing method.
As a further preferable technical scheme, the thickness of the organic coating is 5-30 μm; the organic coating is typically, but not limited to, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm thick. In the preferred embodiment, the organic coating with a thickness of 5-30 μm has good wettability, can reduce internal resistance, improve the electrochemical performance of the battery, and has good electrolyte adsorption capability, and if the organic coating is too thick, even exceeds the thickness of the common diaphragm of the existing lithium ion battery, the organic coating cannot play a role of no diaphragm, which is not beneficial to improving the volume energy density of the lithium ion battery. The organic matter coating is too thin, and the film strength is low after curing, which brings great difficulty to the subsequent battery manufacture.
In a third aspect, an application of the pole piece for the lithium ion battery in the lithium ion battery is provided.
The pole piece for the lithium ion battery coated with the organic coating is applied to the lithium ion battery, so that the lithium ion battery is free of membrane, the battery preparation process is simple, and the battery cost is reduced.
And the positive pole piece and/or the negative pole piece are/is a pole piece for the lithium ion battery.
The lithium ion battery is not provided with a diaphragm, so that the space utilization rate inside the lithium ion battery cell is greatly improved, and the volume energy density of the lithium ion battery is improved.
In a fifth aspect, an application of the lithium ion battery in a smart phone, a digital camera, a notebook computer or an electric vehicle is provided.
The lithium ion battery without the diaphragm can enable digital products to develop towards lighter and thinner directions, and the endurance mileage of the new energy electric vehicle is improved.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
1. Application of organic coating as diaphragm in preparation of lithium ion battery
The organic coating is formed by curing a coating which comprises 20g of vinylidene fluoride-hexafluoropropylene copolymer, 210g of acetone and 34.4g of ethanol.
2. Preparation of the coating
20g of vinylidene fluoride-hexafluoropropylene copolymer powder is added into 210g of acetone solution, and the copolymer powder is heated for 1.2 hours at 50 ℃ after being dissolved to obtain a transparent and uniform mixed solution. 34.4g of ethanol was further added to the mixed solution to form a blended solution, and the resulting blended solution was heated at 50 ℃ for 0.8 hour to obtain a coating material for coating.
3. Pole piece for lithium ion battery
Coating a negative active material layer on the surface of a negative pole piece
Preparing anode slurry: according to the anode active material: conductive agent: mixing the binder at a weight ratio of 95:2:3, and then uniformly mixing the binder with 120 parts of deionized water to obtain negative electrode slurry; the negative active material is graphite, the conductive agent is conductive carbon black SuperP, and the binder is CMC and SBR.
The negative electrode active material layer (2) having a thickness of 150 μm was prepared by coating the positive electrode slurry on the front and back surfaces of a copper foil substrate (1), as shown in fig. 1.
② coating positive active substance layer on the surface of positive pole piece
Preparing positive electrode slurry: according to the positive electrode active material: conductive agent: mixing the binder at a weight ratio of 96:2:2, and then uniformly mixing an NMP (N-methylpyrrolidone) solvent, wherein the weight ratio of NMP to the positive electrode active material is 32.5: 96, obtaining positive electrode slurry; the nickel-cobalt-manganese ternary material is used as a positive electrode active material, the conductive agent is conductive carbon black SuperP and conductive graphite Ks-6 (the mass ratio of the SuperP to the Ks-6 is 1: 1), and the binder is PVDF.
The positive electrode slurry was coated on the front and back surfaces of an aluminum foil substrate (4) to prepare a positive electrode active material layer (5) having a thickness of 220 μm as shown in fig. 1.
Thirdly, coating the prepared coating on the surfaces of the positive plate active material layer (5) and the negative plate active material layer (2) which are rolled and cut by adopting a scraper coating method, preparing an organic coating (6) with the thickness of 20 mu m on the surface of the positive plate active material layer (5), and preparing an organic coating (3) with the thickness of 20 mu m on the surface of the negative plate active material layer (2), as shown in figure 1.
Vacuum baking the coated positive pole piece for 24 hours at 80 ℃; vacuum baking the coated negative pole piece for 24 hours at 60 ℃;
4. lithium ion battery without diaphragm
And manufacturing the positive and negative pole pieces into a battery roll core according to a winding mode, and assembling the battery roll core, the battery shell and the electrolyte into a battery.
Example 2
1. Application of organic coating as diaphragm in preparation of lithium ion battery
The organic coating is formed by curing a coating, wherein the coating comprises 10g of vinylidene fluoride-hexafluoropropylene copolymer, 105g of acetone and 27g of ethanol.
2. Preparation of the coating
10g of vinylidene fluoride-hexafluoropropylene copolymer powder is added into 105g of acetone solution, and the copolymer powder is heated for 1 hour at 50 ℃ after being dissolved to obtain a transparent and uniform mixed solution. Further, 27g of ethanol was added to the mixed solution to form a blended solution, and the resulting blended solution was heated at 50 ℃ for 1 hour to obtain a coating material for coating.
3. Pole piece for lithium ion battery
Coating a negative active material layer on the surface of a negative pole piece
Preparing anode slurry: according to the anode active material: conductive agent: mixing the binder at a weight ratio of 95:2:3, and then uniformly mixing the binder with 120 parts of deionized water to obtain negative electrode slurry; the negative active material is graphite, the conductive agent is conductive carbon black SuperP, and the binder is CMC and SBR.
The anode slurry was coated on the front and back surfaces of a copper foil substrate (1) to prepare an anode active material layer (2) having a thickness of 142 μm, as shown in fig. 2.
② coating positive active substance layer on the surface of positive pole piece
Preparing positive electrode slurry: according to the positive electrode active material: conductive agent: mixing the binder at a weight ratio of 95:2:3, and then uniformly mixing an NMP (N-methylpyrrolidone) solvent, wherein the weight ratio of NMP to the positive electrode active material is 32.5: 95, obtaining positive electrode slurry; the lithium manganate material is used as a positive electrode active material, the conductive agent is conductive carbon black SuperP and conductive graphite Ks-6 (the mass ratio of the SuperP to the Ks-6 is 1: 1), and the binder is PVDF.
The positive electrode slurry was coated on the front and back surfaces of an aluminum foil substrate (4) to prepare a 203 μm thick positive electrode active material layer (5), as shown in fig. 2.
Thirdly, coating the prepared coating on the surface of the rolled and cut active material layer (2) of the negative pole piece by adopting a roll coating method; an organic coating (3) with the thickness of 20 mu m is formed on the surface of the active material layer (2) of the negative pole piece, as shown in figure 2.
And (3) baking the coated negative pole piece for 24 hours in vacuum at 60 ℃.
4. Lithium ion battery without diaphragm
And manufacturing the positive and negative pole pieces into a battery roll core in a lamination mode, and assembling the battery roll core, the battery shell and the electrolyte into a battery.
Example 3
1. Application of organic coating as diaphragm in preparation of lithium ion battery
The organic coating is formed by curing a coating which comprises 10g of vinylidene fluoride-hexafluoropropylene copolymer, 105g of acetone and 34.4g of ethanol.
2. Preparation of the coating
10g of vinylidene fluoride-hexafluoropropylene copolymer powder is added into 105g of acetone solution, and the copolymer powder is heated for 1.5 hours at 50 ℃ after being dissolved to obtain a transparent and uniform mixed solution. 34.4g of ethanol was further added to the mixed solution to form a blended solution, and the resulting blended solution was heated at 50 ℃ for 0.5 hour to obtain a coating material for coating.
3. Pole piece for lithium ion battery
Coating a negative active material layer on the surface of a negative pole piece
Preparing anode slurry: according to the anode active material: conductive agent: mixing the binder at a weight ratio of 95:2:3, and then uniformly mixing the binder with 120 parts of deionized water to obtain negative electrode slurry; the negative active material is graphite, the conductive agent is conductive carbon black SuperP, and the binder is CMC and SBR.
The negative electrode active material layer (2) was formed to have a thickness of 147 μm by coating the negative electrode slurry on the front and back surfaces of the copper foil substrate (1), as shown in fig. 3.
② coating positive active substance layer on the surface of positive pole piece
Preparing positive electrode slurry: according to the positive electrode active material: conductive agent: mixing the binder at a weight ratio of 96:2:2, and then uniformly mixing an NMP (N-methylpyrrolidone) solvent, wherein the weight ratio of NMP to the positive electrode active material is 32.5: 96, obtaining positive electrode slurry; the lithium cobaltate material is used as a main material of the positive electrode active substance, the conductive agent is conductive carbon black SuperP and conductive graphite KS-6 (the mass ratio of the SuperP to the KS-6 is 1: 1), and the binder is PVDF.
The positive electrode slurry was coated on the front and back surfaces of an aluminum foil substrate (4) to prepare a positive electrode active material layer (5) having a thickness of 205 μm, as shown in fig. 3.
Thirdly, coating the prepared coating on the surface of the active material layer (5) of the rolled and cut positive pole piece by adopting a spraying method; an organic coating (6) with the thickness of 20 mu m is formed on the surface of the active material layer (5) of the positive pole piece, as shown in figure 3.
And (3) baking the coated positive pole piece for 24 hours in vacuum at 80 ℃.
4. Lithium ion battery without diaphragm
And manufacturing the positive and negative pole pieces into a battery roll core according to a winding mode, and assembling the battery roll core, the battery shell and the electrolyte into a battery.
Examples 4 to 7
Examples 4-7 differ from example 1 in the amounts of the components in the coating, as shown in Table 1.
TABLE 1 examples 4-7 coating compositions parts by weight
Vinylidene fluoride-hexafluoropropylene copolymer Acetone (II) Ethanol
Example 4 9 portions of 90 portions of 40 portions of
Example 5 11 portions of 120 portions of 15 portions of
Example 6 10 portions of 100 portions of 17 portions of
Example 7 10 portions of 110 portions of 34 portions of
Examples 8 to 10
Examples 8 to 10 differ from example 4 in the kind of solvent and non-solvent in the coating material, as shown in Table 2.
TABLE 2 types of solvents and non-solvents in examples 8-10
Solvent(s) Non-solvent
Example 8 Tetrahydrofuran (THF) N-propanol
Example 9 Acetone (II) Isopropanol (I-propanol)
Example 10 N, N-dimethylformamide Ethylene glycol
The vinylidene fluoride-hexafluoropropylene copolymer can be mixed with the solvent and the non-solvent uniformly by increasing the temperature appropriately during the preparation of the coatings of examples 8-10.
Example 11
Example 11 differs from example 1 in that the negative electrode slurry was applied only to the front surface of the copper foil substrate, and in the same manner, the positive electrode slurry was applied only to the front surface of the positive electrode slurry, and then the coating material was applied to the active material layer surface on the front surface of the positive electrode sheet and the active material layer surface on the front surface of the negative electrode sheet after roll cutting by the doctor blade method, thereby forming an organic coating layer of 20 μm on the surface of the positive electrode active material layer, and forming an organic coating layer of 20 μm on the surface of the negative electrode active material layer.
Vacuum baking the coated positive pole piece for 24 hours at 80 ℃; vacuum baking the coated negative pole piece for 24 hours at 60 ℃;
and manufacturing the positive and negative pole pieces into a battery roll core according to a winding mode, and assembling the battery roll core, the battery shell and the electrolyte into a battery.
Test example 1
Safety tests were carried out on the lithium ion batteries of examples 1 to 11 in accordance with GB/T31485-2015, and the safety performance was shown in Table 3.
Table 3 safety performance test results of lithium ion batteries of examples 1 to 11
Overcharge Acupuncture and moxibustion Extrusion
Example 1 By passing By passing By passing
Example 2 By passing By passing By passing
Example 3 By passing By passing By passing
Example 4 By passing By passing By passing
Example 5 By passing By passing By passing
Example 6 By passing By passing By passing
Example 7 By passing By passing By passing
Example 8 By passing By passing By passing
Example 9 By passing By passing By passing
Example 10 By passing By passing By passing
Example 11 By passing By passing By passing
As can be seen from the test results in table 3, the lithium ion batteries of examples 1 to 11 have higher safety performance. In the needling and overcharge tests, examples 1-11 all passed without the explosive ignition.
It should be understood that the contents not described in detail in the description of the above preparation method are common parameters that can be easily conceived by those skilled in the art, and thus the detailed description thereof may be omitted.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (13)

1. The pole piece for the lithium ion battery is characterized by comprising a current collector, wherein the surface of the current collector is coated with an active substance layer, the surface of the current collector is also coated with an organic substance coating, and the active substance layer is positioned between the organic substance coating and the current collector;
wherein the organic coating is formed by curing a coating;
the coating comprises the following components in parts by weight:
9-11 parts of vinylidene fluoride-hexafluoropropylene copolymer, 90-120 parts of solvent and 15-40 parts of non-solvent;
the organic coating is used as a diaphragm in the preparation of the lithium ion battery;
the non-solvent is at least one of methanol, ethanol, n-propanol and isopropanol;
the thickness of the organic coating is 5-30 μm.
2. The pole piece for the lithium ion battery of claim 1, wherein the coating comprises the following components in parts by weight:
9.5-10.5 parts of vinylidene fluoride-hexafluoropropylene copolymer, 110 parts of solvent 100 and 17-34 parts of non-solvent.
3. The electrode sheet according to claim 1, wherein the solvent is an organic solvent.
4. The electrode sheet of claim 1, wherein the solvent is at least one of acetone, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and dimethylacetamide.
5. The electrode sheet according to claim 1, wherein the solvent is acetone.
6. The electrode sheet according to claim 1, wherein the non-solvent is ethanol.
7. The pole piece for the lithium ion battery as claimed in claim 1 or 2, wherein the coating is obtained by uniformly mixing the vinylidene fluoride-hexafluoropropylene copolymer, the solvent and the non-solvent.
8. The pole piece for the lithium ion battery as claimed in claim 1 or 2, wherein the coating is obtained by adding the vinylidene fluoride-hexafluoropropylene copolymer into the solvent at 45-52 ℃, obtaining a mixed solution of the vinylidene fluoride-hexafluoropropylene copolymer and the solvent after 1-1.5h, then adding the non-solvent, and obtaining the coating after 0.5-1 h.
9. The pole piece for the lithium ion battery according to any one of claims 1 to 6, wherein the pole piece is a positive pole piece or a negative pole piece.
10. The electrode sheet for lithium ion battery according to claim 1, wherein the organic coating layer is applied by one or a combination of two or more methods selected from a doctor blade coating method, a spray coating method, a roll coating method, a casting coating method, and a gravure printing method.
11. Use of a pole piece for a lithium ion battery according to any one of claims 1 to 10 in a lithium ion battery.
12. A lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the positive electrode and the negative electrode are assembled into a battery roll core in a winding or laminating manner, and a positive electrode pole piece and/or a negative electrode pole piece are/is the pole piece for the lithium ion battery in any one of claims 1 to 10.
13. Use of the lithium ion battery of claim 12 in a smartphone, digital camera, laptop computer, or electric vehicle.
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